Bis[2-(pyrrolidin-2-yl)-1H-benzimidazole-κN,N]copper(II) dinitrate dihydrate.

In the title compound, [Cu(C(11)H(13)N(3))(2)](NO(3))(2)·2H(2)O, synthesized by hydro-thermal reaction of Cu(NO(3))(2) and racemic 2-(pyrrolidin-2-yl)-1H-1,3-benzimidazole, the Cu(II) atom lies on an inversion centre. The distorted octa-hedral Cu(II) environment contains two planar trans-related N,N-chelating 2-(pyrrolidin-2-yl)-1H-1,3-benzimidazole ligands in the equatorial plane and two monodentate nitrate anions, which are in weak inter-action with the Cu atom, in the axial positions. The two benzimidazole ligands have opposite configurations (R/S and S/R) and compound is a meso complex. In the crystal, N-H⋯O and O-H⋯O hydrogen bonds generate an infinite three-dimensional network. One methylene group of the pyrrolidine ring is disordered over two position with a 0.56 (3):0.44 (3) occupancy.

Related literature

For physical properties such as the ferroelectric and dielectric behavior of metal-organic coordination compounds, see: Fu et al. (2007 ▶). For the synthesis, see: Aminabhavi et al. (1986 ▶). For related structures, see: Dai & Fu (2008a ▶,b ▶); Fu & Ye (2007 ▶).

Experimental

Crystal data

[Cu(C11H13N3)2](NO3)2·2H2O

M = 598.08

Triclinic,

a = 8.2790 (17) Å

b = 8.4446 (17) Å

c = 9.759 (2) Å

α = 100.37 (3)°

β = 107.15 (3)°

γ = 91.37 (3)°

V = 639.1 (2) Å3

Z = 1

Mo Kα radiation

μ = 0.92 mm−1

T = 298 K

0.35 × 0.30 × 0.15 mm

Data collection

Rigaku Mercury2 diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T min = 0.732, T max = 0.871

6713 measured reflections

2914 independent reflections

2566 reflections with I > 2σ(I)

R int = 0.027

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.101

S = 1.11

2914 reflections

188 parameters

6 restraints

H-atom parameters constrained

Δρmax = 0.33 e Å−3

Δρmin = −0.31 e Å−3

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680901808X/dn2443sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680901808X/dn2443Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Cu(C11H13N3)2](NO3)2·2H2O	Z = 1
Mr = 598.08	F(000) = 311
Triclinic, P1	Dx = 1.554 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.2790 (17) Å	Cell parameters from 2913 reflections
b = 8.4446 (17) Å	θ = 3.4–27.5°
c = 9.759 (2) Å	µ = 0.92 mm−1
α = 100.37 (3)°	T = 298 K
β = 107.15 (3)°	Block, blue
γ = 91.37 (3)°	0.35 × 0.30 × 0.15 mm
V = 639.1 (2) Å3

Rigaku Mercury2 diffractometer	2914 independent reflections
Radiation source: fine-focus sealed tube	2566 reflections with I > 2σ(I)
graphite	Rint = 0.027
Detector resolution: 13.6612 pixels mm-1	θmax = 27.5°, θmin = 3.4°
CCD profile fitting scans	h = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −10→10
Tmin = 0.732, Tmax = 0.871	l = −12→12
6713 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.101	H-atom parameters constrained
S = 1.11	w = 1/[σ2(Fo2) + (0.0352P)2 + 0.444P] where P = (Fo2 + 2Fc2)/3
2914 reflections	(Δ/σ)max < 0.001
188 parameters	Δρmax = 0.33 e Å−3
6 restraints	Δρmin = −0.31 e Å−3

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	1.0000	0.5000	0.5000	0.03289 (14)
O1	0.8537 (3)	0.0645 (3)	0.4119 (3)	0.0643 (6)
O2	0.6487 (3)	0.0360 (3)	0.2118 (3)	0.0745 (7)
O3	0.7605 (3)	0.2727 (3)	0.3222 (3)	0.0647 (6)
N1	0.9102 (2)	0.4814 (2)	0.6652 (2)	0.0329 (4)
N2	0.7676 (3)	0.5950 (3)	0.8117 (2)	0.0406 (5)
H2B	0.7115	0.6647	0.8502	0.049*
N3	0.8509 (3)	0.6877 (2)	0.4834 (2)	0.0345 (4)
H3B	0.9103	0.7701	0.4663	0.041*
N4	0.7551 (3)	0.1246 (3)	0.3161 (2)	0.0425 (5)
C1	0.8109 (3)	0.4496 (3)	0.8525 (3)	0.0383 (6)
C2	0.7753 (4)	0.3760 (4)	0.9580 (3)	0.0507 (7)
H2A	0.7151	0.4256	1.0184	0.061*
C3	0.8337 (4)	0.2263 (4)	0.9686 (3)	0.0552 (8)
H3A	0.8115	0.1721	1.0369	0.066*
C4	0.9250 (4)	0.1551 (4)	0.8794 (3)	0.0564 (8)
H4A	0.9643	0.0545	0.8909	0.068*
C5	0.9603 (4)	0.2272 (3)	0.7737 (3)	0.0467 (6)
H5A	1.0208	0.1769	0.7139	0.056*
C6	0.9014 (3)	0.3778 (3)	0.7609 (2)	0.0348 (5)
C7	0.8291 (3)	0.6078 (3)	0.7009 (3)	0.0338 (5)
C8	0.8131 (3)	0.7461 (3)	0.6234 (3)	0.0380 (6)
H8A	0.8966	0.8350	0.6830	0.046*
C9	0.6378 (4)	0.8083 (5)	0.5821 (4)	0.0658 (9)
H9A	0.5789	0.7940	0.6520	0.079*
H9B	0.6446	0.9216	0.5764	0.079*
C11	0.6832 (4)	0.6571 (4)	0.3660 (3)	0.0542 (8)
H11A	0.6811	0.7192	0.2911	0.065*
H11B	0.6610	0.5435	0.3209	0.065*
O1W	0.5901 (3)	0.7856 (3)	0.9583 (3)	0.0757 (7)
H1WA	0.5045	0.8317	0.8968	0.113*
H1WB	0.6169	0.8451	1.0596	0.113*
C10	0.5552 (12)	0.709 (2)	0.4410 (13)	0.066 (3)	0.56 (3)
H10A	0.4736	0.7698	0.3822	0.079*	0.56 (3)
H10B	0.4948	0.6151	0.4524	0.079*	0.56 (3)
C10'	0.5655 (18)	0.773 (2)	0.4195 (16)	0.055 (3)	0.44 (3)
H10C	0.5642	0.8711	0.3809	0.066*	0.44 (3)
H10D	0.4507	0.7226	0.3896	0.066*	0.44 (3)

	U11	U22	U33	U12	U13	U23
Cu1	0.0347 (2)	0.0409 (3)	0.0285 (2)	0.01231 (17)	0.01597 (17)	0.00874 (17)
O1	0.0575 (13)	0.0570 (13)	0.0686 (14)	0.0016 (10)	−0.0016 (11)	0.0231 (11)
O2	0.0782 (16)	0.0615 (14)	0.0594 (14)	0.0032 (12)	−0.0028 (13)	−0.0098 (11)
O3	0.0681 (15)	0.0449 (12)	0.0709 (15)	0.0090 (10)	0.0053 (12)	0.0119 (11)
N1	0.0356 (10)	0.0360 (10)	0.0300 (10)	0.0063 (8)	0.0148 (8)	0.0052 (8)
N2	0.0427 (12)	0.0473 (12)	0.0368 (11)	0.0108 (10)	0.0227 (10)	0.0027 (9)
N3	0.0368 (11)	0.0351 (10)	0.0355 (11)	0.0066 (8)	0.0161 (9)	0.0077 (8)
N4	0.0372 (12)	0.0490 (13)	0.0411 (12)	0.0057 (10)	0.0151 (10)	0.0025 (10)
C1	0.0386 (13)	0.0454 (14)	0.0311 (12)	−0.0013 (11)	0.0142 (10)	0.0025 (10)
C2	0.0549 (17)	0.0651 (19)	0.0374 (14)	−0.0001 (14)	0.0250 (13)	0.0056 (13)
C3	0.075 (2)	0.0581 (18)	0.0381 (15)	−0.0063 (16)	0.0241 (14)	0.0133 (13)
C4	0.085 (2)	0.0457 (16)	0.0441 (16)	0.0056 (15)	0.0246 (16)	0.0150 (13)
C5	0.0660 (18)	0.0421 (15)	0.0378 (14)	0.0090 (13)	0.0244 (13)	0.0076 (11)
C6	0.0401 (13)	0.0387 (13)	0.0257 (11)	0.0003 (10)	0.0127 (10)	0.0024 (10)
C7	0.0313 (12)	0.0393 (13)	0.0306 (12)	0.0026 (10)	0.0120 (10)	0.0016 (10)
C8	0.0420 (14)	0.0362 (13)	0.0383 (13)	0.0094 (11)	0.0177 (11)	0.0033 (10)
C9	0.064 (2)	0.081 (2)	0.071 (2)	0.0437 (18)	0.0356 (18)	0.0315 (19)
C11	0.0545 (18)	0.0480 (16)	0.0471 (16)	0.0155 (13)	−0.0014 (14)	0.0035 (13)
O1W	0.0743 (16)	0.0971 (18)	0.0527 (13)	0.0449 (14)	0.0207 (12)	0.0000 (12)
C10	0.036 (3)	0.071 (7)	0.086 (5)	0.000 (4)	0.003 (3)	0.032 (5)
C10'	0.041 (5)	0.049 (7)	0.071 (6)	0.018 (5)	0.012 (4)	0.009 (5)

Cu1—N1i	1.9922 (19)	C4—C5	1.384 (4)
Cu1—N1	1.9922 (19)	C4—H4A	0.9300
Cu1—N3	2.032 (2)	C5—C6	1.386 (4)
Cu1—N3i	2.032 (2)	C5—H5A	0.9300
O1—N4	1.241 (3)	C7—C8	1.490 (3)
O2—N4	1.240 (3)	C8—C9	1.520 (4)
O3—N4	1.241 (3)	C8—H8A	0.9800
N1—C7	1.324 (3)	C9—C10	1.438 (13)
N1—C6	1.405 (3)	C9—C10'	1.492 (15)
N2—C7	1.343 (3)	C9—H9A	0.9700
N2—C1	1.382 (3)	C9—H9B	0.9700
N2—H2B	0.8600	C11—C10	1.488 (12)
N3—C8	1.491 (3)	C11—C10'	1.529 (11)
N3—C11	1.499 (3)	C11—H11A	0.9700
N3—H3B	0.9100	C11—H11B	0.9700
C1—C2	1.391 (4)	O1W—H1WA	0.9281
C1—C6	1.397 (3)	O1W—H1WB	0.9827
C2—C3	1.375 (4)	C10—H10A	0.9700
C2—H2A	0.9300	C10—H10B	0.9700
C3—C4	1.383 (4)	C10'—H10C	0.9700
C3—H3A	0.9300	C10'—H10D	0.9700
N1i—Cu1—N1	180.000 (1)	N1—C7—C8	121.5 (2)
N1i—Cu1—N3	97.34 (8)	N2—C7—C8	126.0 (2)
N1—Cu1—N3	82.66 (8)	C7—C8—N3	106.82 (19)
N1i—Cu1—N3i	82.66 (8)	C7—C8—C9	115.3 (2)
N1—Cu1—N3i	97.34 (8)	N3—C8—C9	106.4 (2)
N3—Cu1—N3i	180.00 (12)	C7—C8—H8A	109.4
C7—N1—C6	105.71 (19)	N3—C8—H8A	109.4
C7—N1—Cu1	112.43 (16)	C9—C8—H8A	109.4
C6—N1—Cu1	141.85 (16)	C10—C9—C8	102.8 (6)
C7—N2—C1	107.5 (2)	C10'—C9—C8	108.6 (5)
C7—N2—H2B	126.2	C10—C9—H9A	111.2
C1—N2—H2B	126.2	C10'—C9—H9A	126.7
C8—N3—C11	106.2 (2)	C8—C9—H9A	111.2
C8—N3—Cu1	110.88 (15)	C10—C9—H9B	111.2
C11—N3—Cu1	116.78 (16)	C10'—C9—H9B	87.2
C8—N3—H3B	107.5	C8—C9—H9B	111.2
C11—N3—H3B	107.5	H9A—C9—H9B	109.1
Cu1—N3—H3B	107.5	C10—C11—N3	105.4 (5)
O2—N4—O3	118.9 (2)	N3—C11—C10'	106.2 (5)
O2—N4—O1	119.9 (2)	C10—C11—H11A	110.7
O3—N4—O1	121.2 (2)	N3—C11—H11A	110.7
N2—C1—C2	131.1 (2)	C10'—C11—H11A	88.8
N2—C1—C6	106.1 (2)	C10—C11—H11B	110.7
C2—C1—C6	122.8 (3)	N3—C11—H11B	110.7
C3—C2—C1	116.6 (3)	C10'—C11—H11B	129.2
C3—C2—H2A	121.7	H11A—C11—H11B	108.8
C1—C2—H2A	121.7	H1WA—O1W—H1WB	110.4
C2—C3—C4	121.0 (3)	C9—C10—C11	109.9 (6)
C2—C3—H3A	119.5	C9—C10—H10A	109.7
C4—C3—H3A	119.5	C11—C10—H10A	109.7
C3—C4—C5	122.7 (3)	C9—C10—H10B	109.7
C3—C4—H4A	118.7	C11—C10—H10B	109.7
C5—C4—H4A	118.7	H10A—C10—H10B	108.2
C4—C5—C6	117.1 (3)	C9—C10'—C11	104.9 (8)
C4—C5—H5A	121.5	C9—C10'—H10C	110.8
C6—C5—H5A	121.5	C11—C10'—H10C	110.8
C5—C6—C1	119.8 (2)	C9—C10'—H10D	110.8
C5—C6—N1	132.0 (2)	C11—C10'—H10D	110.8
C1—C6—N1	108.1 (2)	H10C—C10'—H10D	108.8
N1—C7—N2	112.5 (2)
N3—Cu1—N1—C7	−11.34 (17)	Cu1—N1—C7—C8	−0.8 (3)
N3i—Cu1—N1—C7	168.66 (17)	C1—N2—C7—N1	−0.1 (3)
N3—Cu1—N1—C6	168.4 (3)	C1—N2—C7—C8	−179.6 (2)
N3i—Cu1—N1—C6	−11.6 (3)	N1—C7—C8—N3	17.5 (3)
N1i—Cu1—N3—C8	−159.18 (16)	N2—C7—C8—N3	−163.0 (2)
N1—Cu1—N3—C8	20.82 (16)	N1—C7—C8—C9	135.5 (3)
N1i—Cu1—N3—C11	79.0 (2)	N2—C7—C8—C9	−45.1 (4)
N1—Cu1—N3—C11	−101.0 (2)	C11—N3—C8—C7	102.9 (2)
C7—N2—C1—C2	−178.2 (3)	Cu1—N3—C8—C7	−24.9 (2)
C7—N2—C1—C6	0.3 (3)	C11—N3—C8—C9	−20.7 (3)
N2—C1—C2—C3	178.1 (3)	Cu1—N3—C8—C9	−148.6 (2)
C6—C1—C2—C3	−0.2 (4)	C7—C8—C9—C10	−88.1 (7)
C1—C2—C3—C4	0.8 (5)	N3—C8—C9—C10	30.0 (7)
C2—C3—C4—C5	−1.2 (5)	C7—C8—C9—C10'	−112.9 (9)
C3—C4—C5—C6	0.7 (5)	N3—C8—C9—C10'	5.3 (10)
C4—C5—C6—C1	−0.1 (4)	C8—N3—C11—C10	3.6 (8)
C4—C5—C6—N1	−178.1 (3)	Cu1—N3—C11—C10	127.8 (7)
N2—C1—C6—C5	−178.9 (2)	C8—N3—C11—C10'	28.3 (10)
C2—C1—C6—C5	−0.2 (4)	Cu1—N3—C11—C10'	152.6 (9)
N2—C1—C6—N1	−0.4 (3)	C10'—C9—C10—C11	78.5 (18)
C2—C1—C6—N1	178.3 (2)	C8—C9—C10—C11	−28.4 (12)
C7—N1—C6—C5	178.6 (3)	N3—C11—C10—C9	16.2 (12)
Cu1—N1—C6—C5	−1.1 (5)	C10'—C11—C10—C9	−79 (2)
C7—N1—C6—C1	0.4 (3)	C10—C9—C10'—C11	−68.1 (16)
Cu1—N1—C6—C1	−179.4 (2)	C8—C9—C10'—C11	11.8 (14)
C6—N1—C7—N2	−0.2 (3)	C10—C11—C10'—C9	67 (2)
Cu1—N1—C7—N2	179.63 (16)	N3—C11—C10'—C9	−24.6 (14)
C6—N1—C7—C8	179.4 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···O1i	0.91	2.25	2.986 (3)	137
O1W—H1WA···O2ii	0.93	1.92	2.836 (4)	169
O1W—H1WB···O2iii	0.98	1.94	2.861 (3)	155
N2—H2B···O1W	0.86	1.86	2.706 (3)	168

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3B⋯O1i	0.91	2.25	2.986 (3)	137
O1W—H1WA⋯O2ii	0.93	1.92	2.836 (4)	169
O1W—H1WB⋯O2iii	0.98	1.94	2.861 (3)	155
N2—H2B⋯O1W	0.86	1.86	2.706 (3)	168

Symmetry codes: (i) ; (ii) ; (iii) .